Copper-Catalyzed Amination of Polyfluoroarenes via Decarbonylative Metallaphotoredox

The development of methods to form anilines has been a long-standing interest in the synthesis field driven by the prevalence of these motifs in natural products, pharmaceuticals, and functional organic materials. Here, a successful protocol for efficient amination of polyfluoroarenes at ambient temperature using oxamic acids as an attractive amino acid source is reported for the first time. A novel decarbonylative metallaphotoredox mechanism via the photoinduced decarboxylation and the decarbonylation of the copper-carbamoyl complex is proposed on the basis of mechanistic and control experiments. The cooperation of photoredox and transition-metal-catalyzed decarbonylation processes paves the way for the construction of C-N or C-C bonds via decarbonylation of formamides, esters, or aldehydes.